Development of an Aerosol Dynamics Model for Dry Deposition Process Using the Moment Method

An aerosol dynamics model for dry deposition process is developed based on the moment method. Since it is hard to fully apply the moment method to the widely used dry deposition velocity expressions based on the resistance theory, the dry deposition velocity expression by Raupach et al. (2001) Raupach, M. R., Briggs, P. R., Ahmad, N. and Edge, V. E. 2001. Endosulfan Tansport: II. Modeling airborne Dispersal and Deposition by Spray and Vapor. J. Environ. Qual., 30: 729–740. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar] is used. Detailed deposition mechanisms such as Brownian diffusion, gravitational settling, and impaction are considered in the expression. To verify the validity of the derived dynamic equation, aerosol dynamics for the dry deposition process is estimated with the expressions of Raupach et al. (2001) Raupach, M. R., Briggs, P. R., Ahmad, N. and Edge, V. E. 2001. Endosulfan Tansport: II. Modeling airborne Dispersal and Deposition by Spray and Vapor. J. Environ. Qual., 30: 729–740. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar], of Wesely (1989) Wesely, M. L. 1989. Parameterizations of Surface Resistance to Gaseous Dry Deposition in Regional-Scale, Numerical Models. Atmos. Environ., 23: 1293–1304. [Crossref], [Web of Science ®] , [Google Scholar] modified for particles (Seinfeld and Pandis 1998 Seinfeld, J. H. and Pandis, S. N. 1998. Atmospheric Chemistry and Physics, 958–996. New York, , USA: Wiley.  [Google Scholar]), in CMAQ, and with constant value used in RAINS-ASIA. Those expressions give different dynamics. Generally, the result for this study is between the result of modified Wesely's expression and CMAQ. When using the modified Wesely's expression with the number of sections being equal or smaller than 10, the resultant size distribution does not give the peak shape accurately.     

DETECTION OF KNOWN PHOTOCHEMICAL DECOMPOSITION PRODUCTS OF PAH IN PARTICULATE MATTER FROM POLLUTION EPISODES IN SEOUL,KOREA

Over the past two decades, significant efforts have been expended to identify the photochemical decomposition products of the OH radical reactions of various polycyclic aromatic compounds (PAC), such as naphthalene, methylnaphthalenes, acenaphthene and phenanthrene (1 Lane, D. A. and Tang, H. 1994. Photochemical degradation of polycyclic aromatic compounds. I. Naphthalene.. Polycycl. Aromat. Comp, 5(1): 131–138. [Taylor & Francis Online] , [Google Scholar], 2 Bunce, N. J., Liu, L., Zhu, J. and Lane, D.A. 1997. Reaction of naphthalene and its derivatives with hydroxyl radicals in the gas phase.. Environ. Sci. Technol, 31(8): 2252–2259.  [Google Scholar], 3 Sasaki, J., Aschmann, S.M., Kwok, E.S.C., Atkinson, R. and Arey, J. 1997. Products of the gas-phase OH and NO3 radical-initiated reactions of naphthalene.. Environ. Sci. Technol, 31(11): 3173–3179.  [Google Scholar], 4 Sauret-Szczepanski, N. and Lane, D.A. 2004. Smog chamber study of acenaphthene: Gas/particle partition measurements of the products formed by reaction with the OH radical.. Polycycl. Aromat. Comp, 24(3): 161–172. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar], 5 Banceu, C. E., Mihele, C.M., Lane, D.A. and Bunce, N.J. 2001. Reactions of methylated naphthalenes with hydroxyl radicals under simulated atmospheric conditions.. Polycycl. Aromat. Comp, 18(4): 415–426. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar], 6 Wang, L., Atkinson, R. and Arey, J. 2007. Dicarbonyl products of the OH radical-initiated reactions of naphthalene and the C1- and C2-alkylnaphthalenes.. Environ. Sci. Technol, 41(8): 2803–2810.  [Google Scholar], 7 Lee, J. Y. and Lane, D.A. 2009. Unique products from the reaction of naphthalene with the hydroxyl radical. Atmos. Environ., 43: 4886–4893. [Crossref] , [Google Scholar]). Although these parent PAC are predominantly found in the gas phase, many of their oxidation products have been found largely in the particle phase (4 Sauret-Szczepanski, N. and Lane, D.A. 2004. Smog chamber study of acenaphthene: Gas/particle partition measurements of the products formed by reaction with the OH radical.. Polycycl. Aromat. Comp, 24(3): 161–172. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar], 7 Lee, J. Y. and Lane, D.A. 2009. Unique products from the reaction of naphthalene with the hydroxyl radical. Atmos. Environ., 43: 4886–4893. [Crossref] , [Google Scholar], 8 Mihele, C. M., Wiebe, H.A. and Lane, D.A. 2002. Particle formation and gas/particle partition measurements of the products of the naphthalene-OH radical reaction in a smog chamber. Polycycl. Aromat. Comp., 22: 729–736. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]). These products include diones, hydroxy-, and nitrated products as well as many products resulting from ring-opening steps. It is, or should be, the goal of every laboratory study on atmospheric processes to apply the laboratory results to real world samples. To this end, we have obtained particulate matter air samples, as well as some smog episode samples, from Seoul Korea and have searched for the known decomposition products of the above mentioned PAC. To eliminate the use of chlorinated solvents used in the extraction and analysis of particulate matter samples, we have been utilizing the direct thermal desorption of small (4 mm diameter) punches of filters followed by Multidimensional Gas Chromatography-Time of Flight Mass Spectrometry (TD-GCxGC-TOFMS) for the analysis of the desorbed compounds. So far, we have detected 14 of the known decomposition products of naphthalene, acenaphthene and phenanthrene in the Seoul pollution episode samples. These include: 1-hydroxynaphthalene, (E) 2-formylcinnamaldehyde, phthalic anhydride, phthalide, 1,2-naphthalic anhydride, 9-hydroxyphenanthrene and dibenzopyrone.     

Design,synthesis, and preliminary evaluation as antimicrobial activity of novel spiro-1, 3-thiazolidine C-acyclic nucleoside analogs

Synthesis of a new class of 1, 3-thiazolidine nucleoside analogs is described. Reaction of 2-amino-2-deoxy-D-glucopyranose hydrochloride 2 with carbon disulfide yielded 5-hydroxy-4-(D-arabino-1, 2, 3, 4-tetrahydroxybutyl)-thiazolidin-2-thione 3, which on acetylation yielded 5-acetoxy-4-(D-arabino-1, 2, 3, 4-tetraacetoxy-butyl)-thiazolidin-2-thione 4. The acetylated sugar 4 reacted with hydrazonoyl chlorides 1a–f, affording the 5-acetoxy-4-(D-arabino-1, 2, 3, 4-tetraacetoxybutyl)-spiro-1 Chen, H., Fan, Y-H., Natarajan, A., Guo, Y., Iyasere, J., Harbinski, F., Luus, L., Christ, W., Aktas, H. and Halperin, J. A. 2004. Bioorg. Med. Chem. Lett., 14: 5401–5405. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar] 3 Nasr, M. N., Gineinah, M. M. and El-Bendary, E. R. 2003. Arch. Pharm., 336: 560–566. [Crossref] , [Google Scholar]thiazolidine-2,2′ -1 Chen, H., Fan, Y-H., Natarajan, A., Guo, Y., Iyasere, J., Harbinski, F., Luus, L., Christ, W., Aktas, H. and Halperin, J. A. 2004. Bioorg. Med. Chem. Lett., 14: 5401–5405. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar] 3 Nasr, M. N., Gineinah, M. M. and El-Bendary, E. R. 2003. Arch. Pharm., 336: 560–566. [Crossref] , [Google Scholar] 4 Belleau, B., Brasilli, L., Chan, L. and Zacheri, B. 1993. Cameron J. Bioorg. Med. Chem. Lett., 3: 1723–1928. [Crossref], [Web of Science ®] , [Google Scholar]thiadiazole derivatives 8a–f. The antibacterial activity of the novel 1, 3-thiazolidine-2,2′ -spiro- 1 Chen, H., Fan, Y-H., Natarajan, A., Guo, Y., Iyasere, J., Harbinski, F., Luus, L., Christ, W., Aktas, H. and Halperin, J. A. 2004. Bioorg. Med. Chem. Lett., 14: 5401–5405. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar] 3 Nasr, M. N., Gineinah, M. M. and El-Bendary, E. R. 2003. Arch. Pharm., 336: 560–566. [Crossref] , [Google Scholar] 4 Belleau, B., Brasilli, L., Chan, L. and Zacheri, B. 1993. Cameron J. Bioorg. Med. Chem. Lett., 3: 1723–1928. [Crossref], [Web of Science ®] , [Google Scholar]thiadiazole nucleoside analogs is highlighted. All compounds with free NH group in the thiazolidine series 8a–f showed significant biological activity against all the standard strains.     

On the Performance of the Fluctuation Test for Structural Change

Abstract

We discuss the performance of “closed-end” fluctuation tests, used to detect changes in the structural stability of a model, in the case where the time horizon is large and the observations do not possess high enough moments. It is demonstrated via a simulation study that, in the latter case, the choice of the boundary function should take into account the number of moments existing; otherwise the actual size of the test may exceed the nominal level. We suggest an alternative “open-end” fluctuation procedure and study its asymptotic behavior. It turns out that if an improper boundary function is chosen, then the null hypothesis may be rejected even if it is true. This means that an appropriate choice of the boundary function requires some prior information about the tail heaviness of the observations. This is different from the cumulative sum-based monitoring schemes suggested by Chu et al. (1996 Chu , C. S. J. , Stinchcombe , M. and White , H. ( 1996 ). Monitoring Structural Change , Econometrica 64 : 1045 – 1065 .[Crossref], [Web of Science ®] , [Google Scholar]) and further studied by Horváth et al. (2004 Horváth , L. , Hu?ková , M. , Kokoszka , P. , and Steinebach , J. ( 2004 ). Monitoring Changes in Linear Models , Journal of Statistical Planning and Inference 126 : 225 – 251 .[Crossref], [Web of Science ®] , [Google Scholar]).     

Theory of Multi-Nozzle Impactor Stages and the Interpretation of Stage Mensuration Data

We describe a general theory of multi-nozzle cascade impactor stages and show how testers of inhaled drug products, such as metered-dose or dry-powder inhalers, can decide, solely from the stage nozzle dimensions, whether any used impactor is satisfactorily operating within its expected aerodynamic performance range. We first account for the realistic shape of particle collection efficiency curves and show that the effective diameter, described by Roberts and Romay (2005) Roberts D. L.Romay F. J.Relationship of Stage Mensuration Data to the Performance of New and Used Cascade ImpactorsJ. Aerosol Med2005184396–413[Crossref], [PubMed] , [Google Scholar], is sufficiently accurate as the primary indication of the aerodynamic performance.

To ensure that a used impactor is performing in the same aerodynamic range allowed for new impactors, one must also satisfy the other, more secondary factors of cascade impaction aerodynamics, most notably the distance to the collection surface relative to the nozzle diameter. We show what this constraint means in practice for used Next Generation Impactors (NGIs; Marple et al. 2003a Marple V. A.Roberts D. L.Romay F. J.Miller N. C.Truman K. G.Van Oort M.Olsson B.Holroyd M. J.Mitchell J. P.Hochrainer D.Next Generation Pharmaceutical Impactor, Part I: DesignJ. Aerosol Med2003a16283–299[Crossref], [PubMed] , [Google Scholar], b Marple V. A.Olson B. A.Santhanakrishnan K.Mitchell J. P.Murray S. C.Hudson-Curtis B. L.Next Generation Pharmaceutical Impactor—Part II: Archival CalibrationJ. Aerosol Med2003b16[Crossref], [PubMed] , [Google Scholar]; 2004 Marple V. A.Olson B. A.Santhanakrishnan K.Roberts D. L.Mitchell J. P.Hudson-Curtis B. L.Next Generation Pharmaceutical Impactor: A New Impactor for Pharmaceutical Inhaler Testing. Part III. Extension of Archival Calibration to 15 L/minJ. Aerosol Med200417335–343[Crossref], [PubMed] , [Google Scholar]), and show that partially occluded nozzles are the most likely nozzles to fail this test.

Applying this principle that used impactors should perform in the same aerodynamic range as new impactors, we derive constraints on the nozzle diameters of any used NGI (Table 6, main text). We can partially apply this principle to other common impactors used for inhaler testing, such as the Andersen and the Marple-Miller, but are hindered by the absence of a published acceptable range for the distance to the impaction collection surface and by the limited published information on the shape of their stage collection efficiency curves.     

2-Aminothiophenol as building blocks for novel heterocycles

Herein, the chemistry of 2-aminothiophenol has been utilized in the synthesis of several interesting products such as oxidation and reaction with π-deficient compounds. On oxidizing 2-aminothiophenol by sodium hypochlorite furnishes 2-[(2-aminophenyl)-dithio]aniline. Treatment of the obtained product with acetyl chloride affords N-(2-[2-(acetylamino)-phenyl-disulphanyl)-phenyl]acetamide. Reaction of the former acetamide with POCl₃ yields 2-methyl-1,3-benzothiazole. Moreover, (3,4,8,9)-dibenzo-2,7-dithia-5,10-diaza4 Field, L. and Lawson, J. E. 1958. J. Am. Chem. Soc., 80: 838[Crossref], [Web of Science ®] , [Google Scholar] 4 Field, L. and Lawson, J. E. 1958. J. Am. Chem. Soc., 80: 838[Crossref], [Web of Science ®] , [Google Scholar] 4 Field, L. and Lawson, J. E. 1958. J. Am. Chem. Soc., 80: 838[Crossref], [Web of Science ®] , [Google Scholar]propellane is formed on reacting the target 2-aminothiophenol with cyclohexane-1,2-dione, whereas its reactions with electron π-acceptors such as 2,3-dichloro-1,4-naphthoquinone (DCHNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetra-cyanoethylene (TCNE), and 1-(dicyanomethylen)acenaphthen-2-one yield various heterocycles.     

SYNTHESES OF ADDUCTS OF ACTIVE METABOLITES OF CARCINOGENIC POLYCYCLIC AROMATIC HYDROCARBONS WITH 2′-DEOXYRIBONUCLEOSIDES

Syntheses are reported for: (1 Harvey, R. G. 1991. Polycyclic Aromatic Hydrocarbons: Chemistry and Carcinogenicity, Cambridge, , U.K.: Cambridge University Press.  [Google Scholar]) adducts of the quinone metabolites of benzo[a]pyrene (BPQ) and benz[a]anthracene (BAQ) with 2′-deoxyadenosine and 2′-deoxyguanosine; (2 Conney, A. H. 1982. Induction of Microsomal Enzymes by Foreign Chemicals and Carcinogenesis by Polycyclic Aromatic Hydrocarbons. Cancer Res., 42: 4875–4917. [PUBMED][INFOTRIEVE][CSA][PubMed], [Web of Science ®] , [Google Scholar]) ¹⁵ N-labelled analogs of these adducts (four or five nitrogen atoms ¹⁵ N-labelled); (3 Dipple, A. 1994. “Reactions of Polycyclic Aromatic Hydrocarbons with DNA”. In DNA Adducts: Identification and Biological Significance, Edited by: Hemminki, K., Dipple, A., Segerbäck, D., Kadulbar, F. F., Shuker, D. and Bartsch, H. pp. 107–129. IARC Scientific Publication No. 125.  [Google Scholar]) depurinated adducts of BPQ and BAQ with adenine or guanine covalently linked to the N7 or N9 positions of the purine bases; (4 Jeffrey, A. M., Weinstein, I. B., Jennette, K., Grzeskowiak, K., Nakanishi, K., Harvey, R. G., Autrup, H. and Harris, C. 1977. Structures of Benzo[a]pyrene-Nucleic Acid Adducts Formed in Human and Bovine Bronchial Explants. Nature (London)., 269: 348–350. [CSA][CROSSREF][Crossref], [PubMed], [Web of Science ®] , [Google Scholar]) ¹³ C-labelled derivatives of benzo[a]pyrene, BPQ, benzo[a]pyrene trans-7,8-dihydrodiol, and the benzo[a]pyrene anti-diol epoxide (with ¹³ C-atoms at the 5- and 11-positions); and (5 Jennette, K., Jeffrey, A. M., Blobstein, S. H., Beland, F. A., Harvey, R. G. and Weinstein, I. B. 1977. Characterization of Nucleoside Adducts from the in Vitro Reaction of Benzo[a]pyrene-7,8-dihydrodiol-9,10-oxide or Benzo[a]pyrene-4,5-oxide with Nucleic Acids. Biochemistry, 16: 932–938. [PUBMED][INFOTRIEVE][CSA][CROSSREF][Crossref], [PubMed], [Web of Science ®] , [Google Scholar]) depurinated adducts formed by reactions of the benzo[a]pyrene radical-cation at the C ⁸ -, N ⁷ -, and N ⁹ -positions of adenine and guanine.     

DYNAMICS OF IMINE AND ACETOPHENONE DERIVATIVES IN SOLUTION STUDIED BY ONE-DIMENSIONAL DIFFUSION-ORDERED NMR SPECTROSCOPY (DOSY)

This paper describes the usefulness of one-dimensional diffusion-ordered NMR spectroscopy (1D-DOSY) in investigating dynamics and interactions of molecules in solution as well as in analyzing the structure of molecules. We synthesized the three imines, N-benzylidene-4-methylbenzene-Sulfonamide (1 Kondo, K., Kazuta, K., Saitoh, A. and Murakami, Y. 2003. Heterocycles, 59: 97–100.  [Google Scholar]), N-(4-chloro-benzylidene)4-methyl-benzene-sulfonamide (2 Horibe, H., Kazuta, K., Kotoku, M., Kondo, K., Okuno, H., Murakami, Y. and Aoyama, T. 2003. Synlett, : 2047–2051. [Web of Science ®] , [Google Scholar]), and N- (4-methoxybenzylidene)-4-methyl-benzene sulfonamide (3 Horibe, H., Fukuda, Y., Kondo, K., Okuno, H., Murakami, Y. and Aoyama, T. 2004. Tetrahedron, 60: 10701–10709. [Crossref], [Web of Science ®] , [Google Scholar]), and acetophenone (4 Sakamoto, Y., Kondo, K., Tokunaga, M., Kazuta, K., Fujita, H., Murakami, Y. and Aoyama, T. 2004. Heterocycles, 63: 1345–1357. [Crossref], [Web of Science ®] , [Google Scholar]) and its three derivatives, 4-chloroacetophenone (5 Sakamoto, Y., Kondo, K., Onozato, M. and Aoyama, T. 2006. Polycycl. Aromat. Comp., 26: 59–68. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]), 4-nitro-acetophenone (6 Kondo, K., Kazuta, K., Fujita, H., Sakamoto, Y. and Murakami, Y. 2002. Tetrahedron, 58: 5209–5214. [Crossref], [Web of Science ®] , [Google Scholar]), and 4-methoxyaceto -phenone (7 Gostam, T., Morean, C., Jutean, A., Guichard, E. and Delsuc, M. A. 2004. Magn. Reson. Chem., 42: 496–499.  [Google Scholar]). 1D-DOSY was applied to a mixture of compounds (1 Kondo, K., Kazuta, K., Saitoh, A. and Murakami, Y. 2003. Heterocycles, 59: 97–100.  [Google Scholar]), (2 Horibe, H., Kazuta, K., Kotoku, M., Kondo, K., Okuno, H., Murakami, Y. and Aoyama, T. 2003. Synlett, : 2047–2051. [Web of Science ®] , [Google Scholar]), and (3 Horibe, H., Fukuda, Y., Kondo, K., Okuno, H., Murakami, Y. and Aoyama, T. 2004. Tetrahedron, 60: 10701–10709. [Crossref], [Web of Science ®] , [Google Scholar]) and to a mixture of compounds (4 Sakamoto, Y., Kondo, K., Tokunaga, M., Kazuta, K., Fujita, H., Murakami, Y. and Aoyama, T. 2004. Heterocycles, 63: 1345–1357. [Crossref], [Web of Science ®] , [Google Scholar]), (5 Sakamoto, Y., Kondo, K., Onozato, M. and Aoyama, T. 2006. Polycycl. Aromat. Comp., 26: 59–68. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]), (6 Kondo, K., Kazuta, K., Fujita, H., Sakamoto, Y. and Murakami, Y. 2002. Tetrahedron, 58: 5209–5214. [Crossref], [Web of Science ®] , [Google Scholar]), and (7 Gostam, T., Morean, C., Jutean, A., Guichard, E. and Delsuc, M. A. 2004. Magn. Reson. Chem., 42: 496–499.  [Google Scholar]). Although ¹ H NMR chemical shifts of the molecules in the mixtures resembled one another in the surrounding, we could distinguish signals of the individual molecules in each mixture on the basis of the NMR data and the values of the diffusion coefficient. Also, we could found the correlation of the measured diffusion coefficients and the calculated molecular volumes.     

Selective Deflection and Localization of Flowing Aerosols onto a Substrate

Pulsed airflow cued by the fluorescence spectrum of a particular aerosol can be used to distinguish and deflect particles of biological origin out of an aerosol stream, permitting concentration of these particles for subsequent analysis (Pan et al. 2004 Pan, Y. L., Boutou, V., Bottiger, J. R., Zhang, S. S., Wolf, J. P. and Chang, R. K. 2004. A Puff of Air Sorts Bioaerosols for Pathogen Identification. Aerosol Sci. Technol., 38: 598–602. [CROSSREF][CSA][Taylor & Francis Online], [Web of Science ®] , [Google Scholar]). However, these high velocity pulses of air have an inherent tendency to scatter particles, confounding efforts to concentrate these deflected particles for analysis. The ability to concentrate large numbers of biological particles into a small area on a collection substrate is particularly important for more species-specific techniques such as Raman and FTIR (Fourier Transform Infra-Red) spectroscopy, which require long integration times due to their weak signal strength. In the present work, a simple method is developed for deflecting and localizing particles after classification by a pulsed airflow. The concept is both modeled and experimentally tested. A specially designed funnel is used to localize the scattered particles onto an area of substrate as small as 1 mm in diameter. Computational fluid dynamics simulations were performed to investigate the interaction of the pulsed airflow with the deflected particles and the localizing funnel, in order to gain insight into design parameters and operating conditions that affect the efficiency of this technique. The results show that the combination of pulsed airflow with a localizing funnel effectively deflects and localizes the concentrated bioaerosol onto a small area of substrate or an opening of a microfluidic cell.     

Quantification of Carboxylic and Carbonyl Functional Groups in Organic Aerosol Infrared Absorbance Spectra

Atmospheric aerosols are one of the least understood components of the climate system and incur adverse health effects on susceptible populations. Organic aerosols can make up as much as 80% of atmospheric aerosols (Lim and Turpin 2002 Lim, H. J. and Turpin, B. J. 2002. Origins of Primary and Secondary Organic Aerosol in Atlanta: Results’ of Time-Resolved Measurements During the Atlanta supersite experiment. Environ. Sci. Technol., 36: 4489–4496. 10.1021/es0206487[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]), and so its quantification and characterization plays an important role in reducing our uncertainty with regards to aerosol impacts on health and climate. As the number of organic molecules in the atmosphere are diverse in number (Hamilton et al. 2004 Hamilton, J. F., Webb, P. J., Lewis, A. C., Hopkins, J. R., Smith, S. and Davy, P. 2004. Partially Oxidised Organic Components in Urban Aerosol using GCXGC-TOF/MS. Atmos. Chem. Phys., 4: 1279–1290. [Crossref], [Web of Science ®] , [Google Scholar]), we advance a functional group representation of organic molecules as measured by Fourier transform infrared spectroscopy (FTIR) to characterize the chemical composition of particle samples. This study describes and evaluates the algorithm introduced by Russell et al. (2009 Russell, L. M., Takahama, S., Liu, S., Hawkins, L. N., Covert, D. S.Quinn, P. K. 2009. Oxygenated Fraction and Mass of Organic Aerosol from Direct Emission and Atmospheric Processing Measured on the R/V Ronald Brown During TEXAQS/GoMACCS 2006. J. Geophys. Res.-Atmos., 114: D00F05 10.1029/2008JD011275[Crossref], [Web of Science ®] , [Google Scholar]) for apportionment and quantification of oxygenated (carbonyl and hydroxyl) functional groups from infrared absorption spectra. Molar absorptivities for carbonyl and hydroxyl bonds in carboxylic groups are obtained for several dicarboxylic compounds, and applied to a multifunctional compound and mixture to demonstrate the applicability of this method for more complex samples. Furthermore, functional group abundances of two aldehydic compounds, 2-deoxy-d-ribose and glyceraldehyde, atomized from aqueous solution are in quantitative agreement with number of bonds predicted after transformation of these compounds into diols. The procedure for spectra interpretation and quantitative analysis is described through the context of an algorithm in which contributions of background and analyte absorption to the infrared spectrum are apportioned by the superposition of lineshapes constrained by laboratory measurements.

Copyright 2013 American Association for Aerosol Research     

AN IMPROVEMENT TO THE SSF MODEL FOR PREDICTION OF LIGHT PARTICLE DISPERSION

This study investigates the predicted motion of small, light particles using the stochastic separated flow models proposed by Shuen et al. (1983 Shuen , J. S. , Chen , L. D. , and Faeth , G. M. ( 1983 ). Evaluation of a stochastic model of particle dispersion in a turbulent round jet , AIChE J. , 29 , 167 – 170 . [CSA] [CROSSREF] [Crossref], [Web of Science ®] , [Google Scholar]) and Lightstone and Raithby (1998 Lightstone , M. F. and Raithby , G. D. ( 1998 ). A stochastic model of particle dispersion in a turbulent gaseous environment , Combust. Flame , 113 , 424 – 441 . [CSA] [CROSSREF] [Crossref], [Web of Science ®] , [Google Scholar]). Model predictions are compared to the benchmark experiment of Snyder and Lumley (1971 Snyder , W. H. and Lumley , J. L. ( 1971 ). Some measurements of particle velocity autocorrelation functions in a turbulent flow , J. Fluid Mech. , 48 , 41 – 71 . [CSA] [CROSSREF] [Crossref], [Web of Science ®] , [Google Scholar]) for particles released from a point source in grid-generated turbulence. It is found that the predictions of particle velocity variance and dispersion exhibit nonphysical waves. This behavior is explored in order to understand its mathematical basis arising from the model formulation. A modification to the model is presented. The modified model is successful in removing the characteristic waves.     

PENTACYCLIC TRITERPENE CONSTITUENTS OF YELLOW BIRCH BARK FROM QUEBEC*

ABSTRACT

Birch bark represents an abundant, and currently under-utilized, natural resource. Yellow birch (Betula alleghaniensis), the emblem tree of Quebec, is commercially important and one of the most widespread birch species in the province, but the use of its bark is limited. It is only used as a low value fuel source in solid wood products industries. Yellow birch bark triterpene constituents such as lupeol, betulin and betulinic acid have been described to have high biological activity. The yellow birch bark triterpene constituents such as betulin and certain derivatives of this natural substance have demonstrated interesting therapeutic properties. For example, betulinic acid has been shown to possess anti-tumor activity against human melanoma cells both in vitro and in vivo models. Its mechanism of action consists in the induction of apoptosis or cellular suicide in the cancer cells without affecting healthy cells.[14] Pisha, E., Chai, H., Lee, I.-S., Chagwedera, T.E., Farnsworth, N.R., Cordell, G.A., Beecher, C.W.W., Fong, H.H.S., Kinghorn, A.D., Brown, M., Wani, M.C., Wall, M.E., Hieken, T.J., Das Gupta, T.K. and Pezzuto, J.M. 1995. Nature Medicine, 1: 1046[Crossref], [PubMed], [Web of Science ®] , [Google Scholar] These natural products confer added value to this tree. In this study, we investigated the triterpenoid composition of the outer bark of B. alleghaniensis from three locations in Quebec: Saint-Damien de Bellechasse, Saint-Félix-d’Otis, and Duchesnay. Eight triterpenes not previously reported in the bark of yellow birch were detected in this research. The betulonic aldehyde was identified as a new yellow birch bark constituent in bark samples from all sites, while the betulinic aldehyde and the oleanane type triterpenes were only detected in the sample from Saint-Félix-d’Otis. To our knowledge, this is the first time that the oleanane-type triterpenes are identified in yellow birch bark.

     

Pyrido[2,3-d]pyrimidine-2,7-dithiol in heterocyclic synthesis: Synthesis and characterization of several new fused pyridopyrimidine heterocycles

Pyridine-2(1H)-thione 1 reacted with phenyl isothiocyanate to give pyrido[2,3-d]pyrimidine derivative 3. Compound 3 reacted with halogen containing compounds 4a–d and methyl iodide in dimethylformamide/potassium hydroxide solution at room temperature to give 2,7-bisalkylthiopyrido[2,3-b]pyrimidine derivatives 5a–d and 9, respectively. Compounds 5a–d could be cyclized into thienopyrido[2,3-d]pyrimidine derivatives 6a–d by boiling with ethanolic potassium hydroxide solution. Compound 6a reacted with acetic anhydride or formic acid and gave the corresponding pyrimido[4″,5″:4′,5′]thieno[3′,2′:5,6]pyrido[2,3-d]pyrimidine derivatives 8a,b. Compound 9 reacted with hydrazine hydrate to yield pyrazolo[4′,3′:5,6]pyrido[2,3-d]pyrimidine derivative 11 which could be reacted with nitrous acid and dimethylformamide-dimethylacetal (DMF-DMA) and gave the final isolable products corresponding to the pyrazolo[4′,3′:5,6]pyrido[2,3-d]tetrazolo-[5,1-b]pyrimidine and pyrimido[1″,2″:1′,5′]pyrazolo[4′,3′:5,6]pyrido[2,3-d]1 Abbas, A. A., Elneairy, M. A.A. and Mabkhot, Y. N. 2001. J. Chem. Res.(S), 4: 124[Crossref] , [Google Scholar] 2 Riad, B. Y., Negem, A. M., Abdou, S. E. and Daboun, H. A. 1987. Heterocycles, 26: 205[Crossref], [Web of Science ®] , [Google Scholar] 4 Gad-Elkareem, M. A.M. and Abedelhamid, A. O. 2004. Afinidad, 61(513): 427[Web of Science ®] , [Google Scholar]triazolo-[4,3-b] pyrimidine derivatives 13 and 17, respectively. Compound 11 also reacted with some β-dicarbonyl compounds such as acetylacetone (18) and ethyl acetoacetate (20) to yield the corresponding pyrimido[1″,2″:1′,5′]pyrazolo[4′,3′:5,6]pyrido[2,3-d]pyrimidine derivatives 19 and 21, respectively. Finally, compound 11 reacted with chloroacetyl chloride (22) to give the corresponding imidazo[1″′,2″′:1″,5″]pyrazolo[4″,3″:5′,6′]pyrido[3′,2′:5,6]pyrimido[2,1-c]1 Abbas, A. A., Elneairy, M. A.A. and Mabkhot, Y. N. 2001. J. Chem. Res.(S), 4: 124[Crossref] , [Google Scholar] 2 Riad, B. Y., Negem, A. M., Abdou, S. E. and Daboun, H. A. 1987. Heterocycles, 26: 205[Crossref], [Web of Science ®] , [Google Scholar] 4 Gad-Elkareem, M. A.M. and Abedelhamid, A. O. 2004. Afinidad, 61(513): 427[Web of Science ®] , [Google Scholar]triazine derivative 23.     

Mechanical Effect of Acetic Acid Lignin Adsorption on Honeycomb-Patterned Cellulosic Films

Abstract

We have already fabricated honeycomb-patterned cellulosic films with cellulose I and II polymorphisms as a basal framework in order to create an artificial woody cell wall.^{[ 1} Nemoto, J., Uraki, Y., Kishimoto, T., Sano, Y., Funada, R., Obata, N., Yabu, H., Tanaka, M. and Shimomura, M. 2005. Production of mesocopically patterned cellulose film. Bioresour. Technol., 96: 1955–1958.  [Google Scholar] ^{, 2} Uraki, Y., Nemoto, J., Otsuka, H., Tamai, Y., Sugiyama, J., Kishimoto, T., Ubukata, M., Yabu, H., Tanaka, M. and Shimomura, M. 2007. Honeycomb-like architecture produced by living bacteria, Gluconacetobacter xylinus. Carbohydr. Polym., 69: 1–6. [Crossref], [Web of Science ®] , [Google Scholar] ^] The adsorption of an isolated lignin, acetic acid lignin (AL), was attempted onto the honeycomb films not only to develop materials further mimicking the cell wall but also to elucidate the mechanical effect of isolated lignin on the tensile strength of the cellulosic architecture. The tensile strengths of honeycomb-patterned cellulosic films were improved by the AL adsorption. Although the cellulosic films without lignin weakened under high moisture content conditions as compared with those under the low content conditions, the lignin-adsorbed cellulosic film maintained significant tensile strength even under the high content conditions. This result suggests that lignin contributes to reinforce the mechanical strength of cellulose framework, in particular high moisture conditions.     

Numerical Evaluation of the Transfer Function of a Low Pressure DMA by Using the Langevin Dynamic Equation

The effect of Brownian diffusive particle trajectory of nanoparticles on the transfer function of the low pressure Differential Mobility Analyzer (LPDMA) was evaluated by a numerical simulation of the Langevin dynamic equation. The results of the simulation were compared with previously reported experimental results (Seto et al. 1997 Seto, T., Nakamoto, T., Okuyama, K., Adachi, M., Kuga, Y. and Takeuchi, K. 1997. Size Distribution Measurement of Nanometer-Sized Aerosol Particles using DMA under Low-Pressure Conditions. J. Aerosol Sci., 28: 193–206. [CROSSREF][Crossref] , [Google Scholar]; Seol et al. 2000 Seol, K. S., Tsutatani, Y., Camata, R. P., Yabumoto, J., Isomura, S., Okada, Y., Okuyama, K. and Takeuchi, K. 2000. A Differential Mobility Analyzer and A Faraday Cup Electrometer for Operation at 200-930 Pa Pressure. J. Aerosol Sci., 31: 1389–1395. [CSA][CROSSREF][Crossref] , [Google Scholar]) and Stolzenburg's transfer function (1988). As the operational pressure decreased, the peak and FWHM (full width of the transfer function at half of its maximum) values of transfer function, as calculated by numerical simulation, were increased, which was not evident from Stolzenburg's transfer function. In comparison with the experiments of Seto et al., discrepancies in the higher electrical mobility regime than from central mobility were found, which could be caused by the incomplete flow control of their LPDMA. However, the transfer function, as calculated by numerical simulation was in good agreement with experimental results reported by Seol et al., performed with the improved LPDMA at well-controlled operation conditions.     

Methodology for Performance Evaluation of Dust Control Systems with an Application to Electrostatic Precipitators

A general methodology is presented that enables rigorous estimation of the total collection efficiency and the size distribution of particles penetrating dust control systems. This methodology assumes lognormal inlet particle-size distributions and can be used with fractional efficiency formulations that predict, under such conditions, lognormal outlet particle-size distributions. Multimodal inlet particle distributions can be accommodated additively. This methodology is applied to Electrostatic Precipitator Systems (ESPs), with the Nobrega et al. (2004) Nobrega, S. W., Falaguasta, M. C. R. and Coury, J. R. 2004. A Study of a Wire-Plate Electrostatic Precipitator Operating in the Removal of Polydispersed Particles. Braz. J. Chem. Eng., 21(2): 275–284. [Crossref], [Web of Science ®] , [Google Scholar] model selected for predicting their fractional efficiencies. For ease of use, a graphical solution has been developed for the Nobrega et al. fractional efficiency relations, but its availability is not a prerequisite for the application of the general methodology. For the latter, the fractional efficiencies corresponding to three particle diameters need to be estimated and this can be done either graphically or numerically using the model of Nobrega et al. or any other fractional efficiency formulation of interest.

Fine particles emerge as the most important pollutant worldwide in terms of human health, creating thus the need for credible particle size-specific inventories. In line with the above, a generic and rigorous method, capable of producing size-specific emission estimates from uncontrolled and controlled sources, has been developed (Economopoulou and Economopoulos 2001 Economopoulou, A. A. and Economopoulos, A. P. 2001. Method for Estimating Size-Specific Particulate Emission Inventories. J. Environ. Eng., ASCE, 127: 1139–1148. [Crossref], [Web of Science ®] , [Google Scholar]). For controlled sources, this method relies on the development of easy to use models that predict the total efficiency and the lognormal size distribution of particles penetrating the control systems used. Such models have already been developed for dry cyclone separators (Economopoulou and Economopoulos 2002a Economopoulou, A. A. and Economopoulos, A. P. 2002a. Rapid Performance Evaluation and Optimal Sizing of Dry Cyclone Separators. J. Environ. Eng., ASCE, 128: 275–285. [Crossref], [Web of Science ®] , [Google Scholar], 2002b Economopoulou, A. A. and Economopoulos, A. P. 2002b. Size Distribution of Particles Penetrating Dry Cyclone Separators. J. Environ. Eng., ASCE, 128: 919–928. [Crossref], [Web of Science ®] , [Google Scholar]) and venturi scrubbers (Economopoulou and Harrison 2007a Economopoulou, A. A. and Harrison, R. M. 2007a. Graphical Analysis of the Performance of Venturi Scrubbers for Particle Abatement. Part I: Rapid Collection Efficiency Evaluation. Aerosol Sci. Technol., 41: 51–62. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar], 2007b Economopoulou, A. A. and Harrison, R. M. 2007b. Graphical Analysis of the Performance of Venturi Scrubbers for Particle Abatement. Part II: Size Distribution of Penetrating Particles. Aerosol Sci. Technol., 41: 63–74. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]). The present methodology extends the use of the inventory methodology to ESP-controlled sources and, in addition, it provides a generalized basis for covering other types of control systems with any fractional efficiency formulation considered appropriate.     

A Numerical Study of Calm Air Sampling with a Blunt Sampler

The performance of an idealized spherical sampler facing both vertically upwards and downwards in calm air is studied numerically. To describe the air flow around the sampler, both potential and viscous flow models have been adopted. The equations of particle motion are then solved to calculate the aspiration efficiency. The dependence of the aspiration efficiency upon the various parameters of importance in calm air sampling are investigated and compared where possible with the experimental work of Su and Vincent (2003 Su, W. C. and Vincent, J. H. 2003. Experimental Measurements of Aspiration Efficiency for Idealized Spherical Aerosol Samplers in Calm Air. J. Aerosol Sci., 34: 1151–1165. [CSA][CROSSREF][Crossref], [Web of Science ®] , [Google Scholar], 2004a Su, W. C. and Vincent, J. H. 2004a. Experimental Measurements and Numerical Calculations of Aspiration Efficiency for Cylindrical Thin-Walled Aerosol Samplers in Perfectly Calm Air. Aerosol Sci. Tech., 38: 766–781. [CSA][CROSSREF][Taylor & Francis Online], [Web of Science ®] , [Google Scholar], b Su, W. C. and Vincent, J. H. 2004b. Towards a General Semi-Empirical Model for the Aspiration Efficiencies of Aerosol Samplers in Perfectly Calm Air. J. Aerosol Sci., 35: 1119–1134. [CSA][CROSSREF][Crossref] , [Google Scholar]).

It is found that in the case of upwards sampling the bluntness of the sampler only has a significant effect upon aspiration for large sampling velocities, values that would not generally be physically realistic. In the case of downwards sampling an important non-dimensional quantity, B ² R _C , is identified, where B represents the sampler bluntness and R _C represents the gravitational effects. This quantity determines the physical conditions for which aspiration will not occur and also the limiting values of the aspiration efficiency when aspiration does occur. In the case of low sampling velocities a difference is noted between experimental and numerical results for aspiration efficiency raising the need for more experimental data in this area. For both upwards and downwards sampling the semi-empirical models of Su and Vincent (2004b) Su, W. C. and Vincent, J. H. 2004b. Towards a General Semi-Empirical Model for the Aspiration Efficiencies of Aerosol Samplers in Perfectly Calm Air. J. Aerosol Sci., 35: 1119–1134. [CSA][CROSSREF][Crossref] , [Google Scholar] have been modified to account for the information gained from the study. This is particularly important in the downwards sampling case where the modified model is found to agree particularly well with the results obtained.     

Fibrous Filter Efficiency and Pressure Drop in the Viscous-Inertial Transition Flow Regime

Fibrous filter pressure drop and aerosol collection efficiency were measured at low air pressures (0.2–0.8 atm) and high face velocities (5–19 m/s) to give fiber Reynolds numbers lying in the viscous-inertial transition flow regime (1–15). In this regime, contemporary filtration theory based on Kuwabara's viscous flow through an ensemble of fibers underpredicts single fiber impaction by several orders of magnitude. Streamline curvature increases substantially as air stream inertial forces become significant. Dimensionless pressure drop measurements followed the viscous-inertial theory of Robinson and Franklin (1972 Robinson, M. and Franklin, H. 1972. The Pressure Drop of a Fibrous Filter at Reduced Ambient Pressures. J. Aerosol Sci., 3: 413–427. [Crossref] , [Google Scholar]) rather than Darcy's linear pressure–velocity relationship. Sodium chloride and iron nano-agglomerate aerosols were tested to provide a comparison between particles of dissimilar densities and shape factors. Total filter efficiency collapsed when plotted against the particle Stokes number and fiber Reynolds number. Efficiencies were then modeled with an impactor type equation where the cutpoint Stokes number and a steepness parameter described data well in the sharply increasing portion of the curve (20%–80% efficiency). A minimum in collection efficiency was observed at small Stokes numbers and attributed to interception and diffusive effects. The cutpoint Stokes number was a linearly decreasing function of fiber Reynolds number. Single fiber efficiencies were calculated from total filter efficiencies and compared to contemporary viscous flow impaction theory (Stechkina et al. 1969 Stechkina, I. B., Kirsch, A. A. and Fuchs, N. A. 1969. Studies on Fibrous Aerosol Filters—IV. Calculation of Aerosol Deposition in Model Filters in the Range of Maximum Penetration. Ann. Occup. Hyg., 12: 1–8. [Crossref], [PubMed] , [Google Scholar]), and numerical simulations of single fiber efficiencies from the literature. Existing theories underpredicted measured single fiber efficiencies, although comparison is problematic. The assumption of uniform flow conditions for each successive layer of fibers is questionable; thus, the common exponential relationship between single fiber efficiency and total filter efficiency may not be appropriate in this regime.

Copyright 2012 American Association for Aerosol Research     

SPEC: A New Process for Strontium and Cesium Partitioning Utilizing Two Macroporous Silica-Based Supramolecular Recognition Agents Impregnated Polymeric Composites

Abstract

To effectively separate two heat generators Cs(I) and Sr(II) from a highly active liquid waste (HLW), two macroporous silica-based polymeric composites (Calix[4]arene-R14 + M)/SiO₂-P and (DtBuCH18C6 + M)/SiO₂-P were synthesized. It was done by impregnating and immobilizing the supramolecular recognition agent, 1,3-[(2,4-diethylheptyl ethoxy)oxy]-2,4-crown-6-calix[4]arene (Calix[4]arene-R14) or 4,4′,(5′)-di-(tert-butylcyclo hexano)-18-crown-6 (DtBuCH18C6), into the pores of the macroporous SiO₂-P particles with a mean diameter of 50 µm. It was found that in the first column packed with (Calix[4]arene-R14 + M)/SiO₂-P, all of the tested elements were effectively eluted and separated into two groups: (1 Horwitz , E.P. ; Mark , L.D. ; Fisher , D.E. ( 1991 ) SREX: A new process for the extraction and recovery of strontium from acidic nuclear waste stream . Solvent Extr. Ion Exch. , 9 ( 1 ): 1 – 25 .[Taylor & Francis Online], [Web of Science ®] , [Google Scholar]) Na(I), K(I), Sr(II), Ba(II), Rh(III), Ru(III), Pd(II), Zr(IV), RE(III) (La-Lu and Y), and Mo(VI) (Sr-containing group), and (2 Wood , D.J. ; Law , J.D. ( 1997 ) Evaluation of the SREX solvent extraction process for the removal of ⁹⁰Sr and hazardous metal ions from acidic nuclear waste solutions containing high concentrations of interfering alkali metal ions . Sep. Sci. Technol. , 32 ( 1–4 ): 241 – 253 .[Taylor & Francis Online], [Web of Science ®] , [Google Scholar]) Cs(I)-Rb(I) (Cs-group) by eluting with 4.0 M HNO₃ and water, respectively, at 298 K. The heat emitting element Cs(I) flowed into the second group along with Rb(I), while Sr(II) showed no sorption and flowed into the Sr-containing group. In the second column packed with (DtBuCH18C6 + M)/SiO₂-P, the Sr-containing group was separated into (1 Horwitz , E.P. ; Mark , L.D. ; Fisher , D.E. ( 1991 ) SREX: A new process for the extraction and recovery of strontium from acidic nuclear waste stream . Solvent Extr. Ion Exch. , 9 ( 1 ): 1 – 25 .[Taylor & Francis Online], [Web of Science ®] , [Google Scholar]) Na(I), K(I), Rh(III), Ru(III), RE(III) (La-Lu and Y), Pd(II), Zr(IV), and Mo(VI) (non-sorption group), and (2 Wood , D.J. ; Law , J.D. ( 1997 ) Evaluation of the SREX solvent extraction process for the removal of ⁹⁰Sr and hazardous metal ions from acidic nuclear waste solutions containing high concentrations of interfering alkali metal ions . Sep. Sci. Technol. , 32 ( 1–4 ): 241 – 253 .[Taylor & Francis Online], [Web of Science ®] , [Google Scholar]) Sr(II)-Ba(II) (Sr-group), by eluting with 2.0 M HNO₃ and water, respectively. The heat emitting element Sr(II) adsorbed by (DtBuCH18C6 + M)/SiO₂-P flowed into the second group along with Ba(II). Based on the results, a new process entitled SPEC (Strontium/Cesium Partitioning from HLW by Extraction Chromatography) for heat generator partitioning from a simulated highly active liquid waste utilizing two macroporous silica-based supramolecular recognition composites has been developed.     

Indazole,oxathiadiazole, and thiadiazine derivatives from thiosemicarbazides

4-Substituted thiosemicarbazides 1a–c reacted with 2,3-dicyano-5,6-dichloro-1,4-benzoquinone (DDQ, 2), 2,3,5,6-tetrachloro-1,4-benzoquinone (CHL-p, 6) and 2,3-dichloro-1,4-naphthoquinone (DCHNQ, 7) in ethyl acetate with admission of air and form the derivatives of 1,5,2,3-oxathiadiazole 8a–c, indazole 9a–c, 1,3,4-thiadiazine-6-one 10a–c, 1,3,4-thiadiazaphenanthren-9-one 11a–c, naphtho[1,2-e:4,3-è]bis1 Nogami, T., Yoshihara, K. and Nagakura, K. 1972. Bull. Chem. Soc. Jpn., 45: 122[Crossref] , [Google Scholar] 3 Belitskaya, L. D. and Kolesnikov, V. T. 1984. Zh. Org. Khim. (Eng. Translation), 20: 1753 [Google Scholar] 4 Foster, R., Kulevsky, N. and Wanigasekera, D. S. 1974. J. Chem. Soc., Perkin Trans., 1: 1318[Crossref] , [Google Scholar]thiadiazine 12 and dibenzo[b,i]thianthrene-5,7,12,14-tetraone 13. A rationale for the conversions observed is presented.